CN108690195A - Composition for flexible substrate and flexible substrate - Google Patents

Composition for flexible substrate and flexible substrate Download PDF

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Publication number
CN108690195A
CN108690195A CN201810295645.0A CN201810295645A CN108690195A CN 108690195 A CN108690195 A CN 108690195A CN 201810295645 A CN201810295645 A CN 201810295645A CN 108690195 A CN108690195 A CN 108690195A
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formula
base plate
compound
flexible base
bis
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CN108690195B (en
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梁育豪
陈志荣
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Chi Mei Corp
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Chi Mei Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention provides a composition for a flexible substrate and a flexible substrate, which can form a flexible substrate with good phase difference. The composition for a flexible substrate includes: a polymer (A) and a solvent (B). The polymer (A) is obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b), the tetracarboxylic dianhydride component (a) comprising a compound (a1) represented by formula (a-1) and a compound (a2) represented by formula (a-2).

Description

Flexible base plate constituent and flexible base plate
Technical field
The present invention relates to a kind of flexible base plate constituents and flexible base plate more particularly to a kind of flexible base plate to form Object, the flexible base plate of good phases difference is made.
Background technology
In recent years, high-molecular organic material has been widely used in various electronic component or device, to promote electronics member Part or device every characteristic (such as:Electric insulating quality, heat resistance or engineering properties etc.).Wherein, with polyimide polymer (polyimide polymer) is most widely used, because it is excellent with good engineering properties and good electrical properties etc. Characteristic, and it is preferred by relevant industry.
WO 2009/107429 discloses a kind of polyimides predecessor constituent of transparent soft substrate.The polyamides is sub- Amine predecessor is reacted with tetracarboxylic dianhydride and is made using diamines (including fluorine-containing benzidine and Isosorbide-5-Nitrae-cyclohexanediamine), and above-mentioned group The flexible base plate of high transparency can be formed at object.However, above-mentioned polyimides predecessor in heat hardening formed polyimides when, It tends to have the bad problem of phase difference to generate, and cannot be satisfied the demand of industry.
Therefore, a kind of flexible base plate constituent and flexible base plate need be provided, to improve existing flexible base plate with forming The defect of object and flexible base plate.
[Zhuan Liwenxian ]
[Patent document 1]WO 2009/107429A1
Invention content
In view of this, the present invention provides a kind of flexible base plate constituent, it can using the flexible base plate constituent Improve the bad problem of the phase difference of flexible base plate.
The present invention provides a kind of flexible base plate constituent, including:Polymer (A) and solvent (B).Wherein, polymer (A) it is to be reacted by mixture and obtained, mixture includes tetracarboxylic dianhydride's component (a) and diamines component (b).Tetracarboxylic dianhydride's group Part (a) includes the compound (a1) indicated by formula (a-1) and by formula (a-2) compound represented (a2):
In formula (a-1), R respectively independently indicates that carbon number is 1 to 6 alkylidene;RXIndicate bivalent aliphatic cyclic hydrocarbon radical, it is described Bivalent aliphatic cyclic hydrocarbon radical is the bilvalent radical for being unsubstituted or replacing through halogen atom, straight-chain alkyl or branched alkyl.
In formula (a-2), R1Indicate the alkyl that hydrogen atom or carbon number are 1 to 6;R2Respectively it is independent indicate hydrogen atom, methyl or Ethyl group.
In one embodiment of this invention, in above-mentioned formula (a-1), RxWith the structure as shown in formula (a-1-x):
In formula (a-1-x), m indicates 0 to 4 integer;RZRespectively independent expression halogen atom, the straight-chain that carbon number is 1 to 4 Alkyl, the branched alkyl that carbon number is 1 to 4 or a plurality of RZIt is interconnected to form cyclic structure.
In one embodiment of this invention, in above-mentioned formula (a-1), R respectively independently indicates that carbon number is 1 to 3 alkylidene.
In one embodiment of this invention, the total mole number for being based on tetracarboxylic dianhydride's component (a) is 100 moles, by formula (a- 1) usage amount of the compound (a1) indicated is 15 to 85 moles, and the usage amount of the compound (a2) indicated by formula (a-2) is 15 To 85 moles.
In one embodiment of this invention, the total usage amount for being based on polymer (A) is 100 parts by weight, the use of solvent (B) Amount is 200 to 2000 parts by weight.
In one embodiment of this invention, at 25 DEG C, the viscosity of flexible base plate constituent be 100cps extremely 20000cps。
The present invention more provides a kind of flexible base plate, including such as above-mentioned flexible base plate constituent.
Based on above-mentioned, of the invention flexible base plate with constituent because containing specific polymer (A), it is thus possible to improve soft The bad problem of the phase difference of property substrate.
To make the foregoing features and advantages of the present invention clearer and more comprehensible, special embodiment below is described in detail below.
Specific implementation mode
<Flexible base plate Zu Chengwu >
The present invention provides a kind of flexible base plate constituent, including:Polymer (A) and solvent (B).In addition, optionally, Flexible base plate constituent can further include additive (C).
It will be detailed below each ingredient of the flexible base plate constituent for the present invention.
Polymer (A)
Polymer (A) is the arbitrary combination selected from polyamic acid resin, polyimide resin or above-mentioned resin.And polymer It (A) can be by including wherein tetracarboxylic dianhydride's group obtained by the mixture reaction of tetracarboxylic dianhydride's component (a) and diamines component (b) Part (a), diamines component (b) and the method for preparing polymer (A) are as described below.
Tetracarboxylic dianhydride's component (a)
Tetracarboxylic dianhydride's component (a) includes the compound (a1) indicated by formula (a-1), the compound indicated by formula (a-2) (a2) and other tetracarboxylic dianhydride's compounds (a3).
The compound (a1) indicated by formula (a-1)
The compound (a1) indicated by formula (a-1) is as follows:
In formula (a-1), R respectively independently indicates that carbon number is 1 to 6 alkylidene;RXIndicate bivalent aliphatic cyclic hydrocarbon radical, it is described Bivalent aliphatic cyclic hydrocarbon radical is the bilvalent radical for being unsubstituted or replacing through halogen atom, straight-chain alkyl or branched alkyl.
The straight-chain alkyl or branched alkyl replaced in bivalent aliphatic cyclic hydrocarbon radical is preferably saturated hydrocarbyl.Described two Valence alicyclic hydrocarbon base can be by monocycle, the condensed ring, the polycyclic, loop coil (Spiro compound) that are made of 2 or more rings Or ring assembly alkyl.Preferably, RXCarbon number can be 3 to 15.
Specifically, RXPreferably can be cyclobutane, pentamethylene, hexamethylene, cycloheptane, cyclooctane, norbornene (Norbornene), dicyclopentadiene (Dicyclopenta diene), adamantane (Adamantane), or it is selected from hydrogenated naphthalene The alicyclic hydrocarbon of ring and A Hydrogenated Bisphenol A removes the bivalent aliphatic cyclic hydrocarbon radical formed after hydrogen atom.Above-mentioned bivalent aliphatic Cyclic hydrocarbon radical can be through halogen atom, straight-chain alkyl or branched alkyl (preferably saturated hydrocarbyl) substitution.
In one embodiment, RxIt preferably can be the bilvalent radical with the structure as shown in formula (a-1-x):
In formula (a-1-x), m indicates 0 to 4 integer;RZRespectively independent expression halogen atom, the straight-chain that carbon number is 1 to 4 Alkyl, the branched alkyl that carbon number is 1 to 4 or a plurality of RZIt is interconnected to form cyclic structure.If in above-mentioned formula (a-1) RxStructure with such as formula (a-1-x) is then formed by the phase difference of flexible base plate more preferably.
In a preferred example, R indicates that carbon number is 1 to 3 alkylidene.If the R in above-mentioned formula (a-1) indicates that carbon number is 1 To 3 alkylidene, then the phase difference of flexible base plate is formed by more preferably.
It will be described below the synthetic method of the compound (a1) indicated by formula (a-1).In one embodiment, above-mentioned by formula (a-1) indicate compound (a1) system by chlorination trimellitic anhydride (Trimellitic anhydride chloride) with fat Race's dihydroxy compounds is reacted and is made, wherein organic with acetonitrile (Acetonitrile), propionitrile (Propanenitrile) etc. Nitrile is as reaction dissolvent.
The specific example of above-mentioned aliphatic dihydroxy compounds may include hexamethylene -1,4- diyl dimethanols (cyclohexane-1,4-diyldimethanol), 2- (4- (hydroxymethyl) cyclohexyl) propyl alcohol (2- (4- (hydroxymethyl) cyclohexyl) propan-1-ol), hexamethylene -1,3- diyl dimethanols (cyclohexane-1,3- Diyldimethanol), 1,1 '-(hexamethylene -1,4- diyls) diethanol (1,1'-(cyclohexane-1,4-diyl) Diethanol), (2- hexahydrotoluene -1,4- diyls) dimethanol ((2-methylcyclohexane-1,4-diyl) Dimethanol), (2- chlorine hexamethylene -1,4- diyls) dimethanol ((2-chloro cyclohexane-1,4-diyl) Dimethanol), 2- (3- (hydroxymethyl) cyclohexyl) propyl alcohol (2- (3- (hydroxymethyl) cyclohexyl) propan- 1-ol), 3- (4- (hydroxymethyl) cyclohexyl) propyl alcohol (3- (4- (hydroxylmethyl) cyclohexyl) propan-1- Ol), 5- thirds butyl -1,3- cyclohexanedimethanols (5-tert-butyl-1,3-cyclohexanedimethanol), 3- (2- (hydroxymethyl) cyclohexyl) propyl alcohol (3- (2- (hydroxymethyl) cyclohexyl) propan-1-ol), 1,4- hexamethylenes Two butanol (1,4-cyclohexanedibutanol), two hexanol of 1,4- hexamethylenes (1,4-cyclohexanedihexanol), 2- (5- (hydroxymethyl) Shuan Huans &#91;2.2.1&#93;Heptane -2- bases) propyl alcohol (2- (5- (hydroxymethyl) bicyclo&#91;2.2.1&#93; Heptan-2-yl) propan-1-ol), Shuan Huan &#91;2.2.1&#93;Heptane -1,4- diyl dimethanols (bicyclo&#91;2.2.1&#93; Heptane-1,4-diyldimethanol), 1,1 '-(Shuan Huan &#91;2.2.2&#93;Octane -1,4- diyls) diethanol (1,1'- (bicycle&#91;2.2.2&#93;Octane-1,4-diyl) bis (ethan-1-ol)), 3- (6- (hydroxymethyl) Shuan Huans &#91;2.2.1&#93;Heptan Alkane -2- bases) propyl alcohol (3- (6- (hydroxymethyl) bicyclo&#91;2.2.1&#93;Heptan-2-yl) propan-1-ol), (decahydro Change naphthalene -1,4- diyls) dimethanol ((decahydro naphthalene-1,4-diyl) dimethanol), (decahydronaphthalenes -2, 3- diyls) dimethanol ((decahydro naphthalene-2,3-diyl) dimethanol), 2- (4- (hydroxymethyl) eight Hydrogen -1H- indenes -5- bases) ethyl alcohol (2- (4- (hydroxy methyl) octahydro-1H-inden-5-yl) ethanol), 2- (3- (hydroxymethyl) adamantane -1- bases) ethyl alcohol (2- (3- (hydroxyl methyl) adamantan-1-yl) ethanol), 2,2'(adamantane -1,3- diyls) diethanol (2,2'(adamantane-1,3-diyl) diethanol), (decahydronaphthalenes- 2,6- diyls) dimethanol ((decahydronaphthalene-2,6-diyl) dimethanol), octahydro -4,7- methylene - 1H- indenes -2,5- dimethanols (octahydro-4,7-methano-1H-indene-2,5-dimethanol) or 1,3- pentamethylene Two butanol (1,3-cyclopentanedibutanol) etc..
In an example, the usage amount of aforementioned organic nitrile is can dissolve above-mentioned chlorination trimellitic anhydride and aliphatic dihydroxy The amount of based compound is advisable.The usage amount that can dissolve the organic nitrile of chlorination trimellitic anhydride is usually the weight of chlorination trimellitic anhydride 1 times to 3 times, preferably 1.5 times to 2 times of amount.Furthermore the usage amount that can dissolve the organic nitrile of aliphatic dihydroxy compounds is logical Often it is 7 times to 12 times, preferably 9 times to 10 times of the weight of aliphatic dihydroxy compounds.
Due to the by-product for the hydrochloride that during the reaction, will produce indissoluble, so that the quality decline of finished product, if Above-mentioned by-product is excessive, is unfavorable for considering economically.Therefore, in above-mentioned reaction process, hydrochloric acid agent for capturing can be used.It is above-mentioned Hydrochloric acid agent for capturing can be any existing salt for dissolving in organic nitrile, wherein being again preferable with pyridine.Above-mentioned salt can also mix Together in the organic nitrile containing aliphatic dihydroxy compounds.
In addition, the molar ratio of chlorination trimellitic anhydride and aliphatic dihydroxy compounds is preferably 2.1 to 2.4.Furthermore it is preceding The molar ratio of the salt and chlorination trimellitic anhydride of stating hydrochloric acid agent for capturing is preferably 1.0 to 1.2.
In an example, the organic nitrile solution of above-mentioned aliphatic dihydroxy compounds is instilled into having for chlorination trimellitic anhydride In machine nitrile solution, to start to react.At this point, the pyridine system as hydrochloric acid agent for capturing is dissolved in the organic of aliphatic dihydroxy compounds In nitrile solution.If in addition, contrary to the above, the organic nitrile solution of chlorination trimellitic anhydride is instilled into aliphatic dihydroxy compounds Organic nitrile solution in, be easier to generate by-product.Therefore, the organic nitrile solution of aliphatic dihydroxy compounds is instilled into chlorination Mode in the organic nitrile solution of trimellitic anhydride is advisable.
The step of above-mentioned instillation, carries out at a temperature of lying in 0 DEG C to 40 DEG C, preferably 5 DEG C to 25 DEG C.The step of instillation, is simultaneously No time limit, only the instillation speed of timing can be advisable under predetermined temperature.After the step of completing above-mentioned instillation, extremely at 15 DEG C It is reacted 1 hour to 10 hours at 40 DEG C, above-mentioned temperature is preferably 20 DEG C to 30 DEG C.
After the completion of reaction, the solid of the compound generated (a1) is filtered and recycled.The hydrochloride by-product generated, Preferable kenel is pyridine hydrochloride, is to be dissolved in organic nitrile, therefore filtered out by separableization by by above-mentioned reaction solution Close object (a1) and by-product.
The solid of above compound (a1) is cleaned with organic solvent then, and then can get the compound (a1) of high-purity.Again Person, can warming compounds (a1), be allowed to be dissolved in organic solvent.There is no particular restriction for above-mentioned organic solvent, only with dissolvableization Closing object (a1) is advisable.Specifically, above-mentioned organic solvent preferably can be n,N-Dimethylformamide (N, N- dimethylformamide;DMF), DMAC N,N' dimethyl acetamide or above-mentioned arbitrary combination.The usage amount of organic solvent can be 2.5 times to 5 times of the solid weight of compound (a1), preferably 3 times to 4 times.
What is illustrated is, it is however generally that, if present invention organic solvent referred to herein using the organic solvent of technical grade, It may contain a small amount of moisture.Above-mentioned moisture may generate the hydrolyzable object of compound (a1).However, a small amount of hydrolyzable Object can remove when recrystallization removes filtrate, and influence is had no on the quality of product.In other words, it uses and removes water if yield is improved Solvent is unfavorable for considering in cost.It is therefore advantageous to for using technical grade organic solvent, and add the acetic anhydride of 1 mass % Using as dehydrating agent.The compound (a1) indicated by formula (a-1) can be made accordingly, even if having by-product generation, to compound (a1), purity only has small influence, therefore can have both yield and purity.
Organic solvent dissolved compound (a1), temperature can be 60 DEG C to 110 DEG C, preferably 70 DEG C to 85 DEG C.If above-mentioned Temperature it is excessively high, obtained liquid crystal orienting film can be made to have the doubt of discoloration.It on the other hand, can not if above-mentioned temperature is too low Reach good refining effect.
After being dissolved compound (a1) using organic solvent, cooling above-mentioned solution makes compound (a1) recrystallization be precipitated.On It can be -10 DEG C to 30 DEG C, preferably 5 DEG C to 25 DEG C to state cooling temperature.If above-mentioned temperature is too low, it is more difficult to mobile knot be precipitated Crystalline substance, and then increase the degree of difficulty of processing.If above-mentioned temperature is excessively high, the yield of product declines and does not meet considering economically.
The crystalline solid being precipitated is filtered, to detach compound (a1).The compound (a1) separated is then with organic solvent Cleaning.Aliphatic ketone, ethers or aromatic hydrocarbon etc. can be used in above-mentioned organic solvent.For example, above-mentioned aliphatic ketone can be Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc..Above-mentioned ethers may be, for example, that tetrahydrofuran, methyl-isobutyl ether or methyl are different Propyl ether etc..It is above-mentioned it is aromatic hydrocarbon may be, for example, benzene,toluene,xylene or ethylbenzene etc..
Tetracarboxylic dianhydride's series of compounds after cleaning carries out being dried under reduced pressure for 24 hours at 80 DEG C, to obtain high-purity Compound (a1).
The compound (a1) indicated by formula (a-1) can be listed below formula (a-1-1) to formula (a-1-24) compound represented:
Total mole number based on tetracarboxylic dianhydride's component (a) is 100 moles, the compound (a1) indicated by formula (a-1) Usage amount is 15 to 85 moles, preferably 20 to 80 moles, more preferably 25 to 75 moles.
If the compound (a1) indicated by formula (a-1) is not used with constituent for flexible base plate, it is formed by flexible base plate Phase difference it is bad.
The compound (a2) indicated by formula (a-2)
The compound (a2) indicated by formula (a-2) is as follows:
In formula (a-2), R1Indicate the alkyl that hydrogen atom or carbon number are 1 to 6;R2Respectively it is independent indicate hydrogen atom, methyl or Ethyl group.
The compound (a2) indicated by formula (a-2) can be listed below formula (a-2-1) to formula (a-2-14) compound represented:
Total mole number based on tetracarboxylic dianhydride's component (a) is 100 moles, the compound (a2) indicated by formula (a-2) Usage amount is 15 to 85 moles, preferably 20 to 80 moles, more preferably 25 to 75 moles.
If the compound (a1) indicated by formula (a-2) is not used with constituent for flexible base plate, it is formed by flexible base plate Phase difference it is bad.
Other tetracarboxylic dianhydride's compounds (a3)
Other tetracarboxylic dianhydride's compounds (a3) include aliphatic tetracarboxylic dianhydride compound, two anhydridization of Alicyclic tetracarboxylic acid Close object, aromatic tetracarboxylic acid's dianhydride compound, the tetracarboxylic dianhydride's compound indicated to formula (a-3-6) by formula (a-3-1) and Fluorine-containing tetracarboxylic dianhydride's compound (fluorine-containing tetracarboxylic dianhydride Compound) etc..
The concrete example of aliphatic tetracarboxylic dianhydride's compound may include but be not limited to ethane tetracarboxylic dianhydride (ethane Tetracarboxylic dianhydride), butane tetracarboxylic acid dianhydride (butane tetracarboxylic ) or the combination of above compound dianhydride.
The concrete example of Alicyclic tetracarboxylic acid dianhydride compound may include but be not limited to 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- Two chloro- 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3, It is 4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylics dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydrides, suitable Formula -3,7- dibutyl suberyl -1,5- diene -1,2,5,6- tetracarboxylic dianhydrides, 2,3,5- tricarboxylics cyclopentyl acetic acid dianhydride or The combination of above compound.
Alicyclic tetracarboxylic acid dianhydride compound also may include bicyclic ring system Alicyclic tetracarboxylic acid dianhydride compound (bicyclic alicyclic tetracarboxylic dianhydride compound).Preferably, bicyclic ring system Alicyclic tetracarboxylic acid dianhydride The tetravalence bridged hydrocarbon groups (bridged hydrocarbon group) that compound is 7 to 9 with total atom number mesh, and four valence bridges The bridge atom number of bridge (bridge) is 1 or 2 one of in hydrocarbyl group.
The concrete example of bicyclic ring system Alicyclic tetracarboxylic acid dianhydride compound may include, but are not limited to Shuan Huan &#91;2.2.1&#93;Heptane -2, 3,5,6- tetracarboxylic dianhydrides, 7- Dan Zashuanhuans &#91;2.2.1&#93;Heptane -2,3,5,6- tetracarboxylic dianhydrides, 7- Yang Zashuanhuans &#91;2.2.1&#93;Heptan Alkane -2,3,5,6- tetracarboxylic dianhydrides, 7- thia Shuan Huans &#91;2.2.1&#93;Heptane -2,3,5,6- tetracarboxylic dianhydrides, 6- (carboxymethyl) are bicyclic &#91;2.2.1&#93;Heptane -2,3,5- tricarboxylic acids -2,3,5,6- dianhydrides, Shuan Huan &#91;2.2.2&#93;It is octane -2,3,5,6- tetracarboxylic dianhydrides, bicyclic &#91;2.2.2&#93;Octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, Shuan Huan &#91;2.2.2&#93;It is octyl- 5- alkene -1,2,7,8- tetracarboxylic dianhydrides, bicyclic &#91;2.2.2&#93;Oct-2-ene -2,3,5,6- tetracarboxylic dianhydrides, 7- Dan Zashuanhuans &#91;2.2.2&#93;Octane -2,3,5,6- tetracarboxylic dianhydrides, 7- Yang Zashuanhuan &#91;2.2.2&#93;Octane -2,3,5,6- tetracarboxylic dianhydrides, 7- thia Shuan Huans &#91;2.2.2&#93;Octane -2,3,5,6- tetrabasic carboxylic acids two Acid anhydride, Shuan Huan &#91;3.2.1&#93;Octane -2,3,5,6- tetracarboxylic dianhydrides, Shuan Huan &#91;3.2.1&#93;Octane -2,4,5,6- tetracarboxylic dianhydrides, 7- nitrogen Miscellaneous Shuan Huan &#91;3.2.1&#93;Octane -2,3,5,6- tetracarboxylic dianhydrides, 7- Dan Zashuanhuans &#91;3.2.1&#93;Octane -2,4,5,6- tetrabasic carboxylic acids two Acid anhydride, 7- Yang Zashuanhuans &#91;3.2.1&#93;Octane -2,3,5,6- tetracarboxylic dianhydrides, 7- Yang Zashuanhuans &#91;3.2.1&#93;Octane -2,4,5,6- four Carboxylic acid dianhydride, 7- thia Shuan Huans &#91;3.2.1&#93;Octane -2,3,5,6- tetracarboxylic dianhydrides, 7- thia Shuan Huans &#91;3.2.1&#93;Octane -2,4, 5,6- tetracarboxylic dianhydrides, Shuan Huan &#91;3.2.2&#93;Nonane -2,3,6,7- tetracarboxylic dianhydrides, Shuan Huan &#91;3.2.2&#93;Nonane -2,4,6,7- four Carboxylic acid dianhydride, Shuan Huan &#91;3.2.2&#93;Nonyl- 8- alkenyl -2,3,6,7- tetracarboxylic dianhydrides, Shuan Huan &#91;3.2.2&#93;Alkenyl -2,4,6 nonyl- 8-, 7- tetracarboxylic dianhydrides, 8- Dan Zashuanhuans &#91;3.2.2&#93;Nonane -2,3,6,7- tetracarboxylic dianhydrides, 8- Dan Zashuanhuans &#91;3.2.2&#93;Nonane- 2,4,6,7- tetracarboxylic dianhydrides, 8- Yang Zashuanhuans &#91;3.2.2&#93;Nonane -2,3,6,7- tetracarboxylic dianhydrides, 8- Yang Zashuanhuans &#91;3.2.2&#93; Nonane -2,4,6,7- tetracarboxylic dianhydrides, 8- thia Shuan Huans &#91;3.2.2&#93;Nonane -2,3,6,7- tetracarboxylic dianhydrides or 8- thias are bicyclic &#91;3.2.2&#93;Nonane -2,4,6,7- tetracarboxylic dianhydrides etc..
The concrete example of aromatic tetracarboxylic acid's dianhydride compound may include but be not limited to 3,4- dicarboxyl -1,2,3,4- tetrahydrochysenes Naphthalene -1- ambers acid dianhydride, the equal tetracarboxylic dianhydride of benzene, 2,2',3,3'Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-hexichol first Ketone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydrides, 1,4,5,8- naphthalene tetracarboxylic acids dianhydride, 2,3,6,7- naphthalene tetracarboxylic acids Dianhydride, 3,3 ' -4,4 '-diphenylethane tetracarboxylic dianhydrides, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydrides, 3, 3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydrides, 1,2,3,4- furans tetracarboxylic dianhydride, 2,3,3',4'Diphenyl ether tetrabasic carboxylic acid two Acid anhydride, 3,3',4,4'Diphenyl ether tetracarboxylic dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides, 2,3,3', 4'Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'Diphenyl sulfide tetracarboxylic dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) Diphenyl sulfone dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl propane dianhydride (4,4 '-bis (3,4-dicarboxy Phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dianhydride, 3,3 ', 4,4 '-biphenyltetracaboxylic dianhydrides, bis- (phthalic acid) phosphniline oxide dianhydrides, p-phenylene-bis- (triphenylbenzene diacid) two Bis- (triphenylbenzene diacid) dianhydrides of acid anhydride,-phenylene -, bis- (triphenylbenzene diacid) -4,4 '-diphenyl ether dianhydrides, bis- (triphens Base phthalic acid) -4,4 '-diphenyl methane dianhydrides, ethylene glycol-bis- (dehydration trimellitates), propylene glycol-is bis- (is dehydrated inclined benzene three Acid esters), 1,4- butanediols-bis- (dehydration trimellitate), 1,6-HD-bis- (dehydration trimellitates), 1,8- ethohexadiols- Bis- (dehydration trimellitates), bis- (4- hydroxyphenyls) propane-of 2,2- bis- (dehydration trimellitates), 2,3,4,5- tetrahydrofurans four Carboxylic acid dianhydride, 1,3,3a, 4,5,9b- hexahydros -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-Nai Bing &#91;1,2-c&#93;Furans- 1,3- diketone { (1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho &#91;1,2-c&#93;Furan-1,3-dione) }, 1,3,3a, 4,5,9b- hexahydro -5- methyl -5- (two side oxygroup -3- furans of tetrahydrochysene -2,5- Mutter base)-Nai Bing &#91;1,2-c&#93;Furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -5- ethyls -5- (two side oxygen of tetrahydrochysene -2,5- Base -3- furyls)-Nai Bing &#91;1,2-c&#93;Furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -7- methyl -5- (tetrahydrochysene -2,5- Two side oxygroup -3- furyls)-Nai Bing &#91;1,2-c&#93;Furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -7- ethyls -5- (four Two side oxygroup -3- furyls of hydrogen -2,5-)-Nai Bing &#91;1,2-c&#93;Furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- first Base -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-Nai Bing &#91;1,2-c&#93;Furans -1,3- diketone, 1,3,3a, 4,5,9b- six Hydrogen -8- ethyls -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-Nai Bing &#91;1,2-c&#93;Furans -1,3- diketone, 1,3,3a, 4, 5,9b- hexahydro -5,8- dimethyl -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-Nai Bing &#91;1,2-c&#93;Furans -1,3- two The aromatic tetracarboxylic acids two such as ketone, 5- (bis- side oxygroup tetrahydrofuran bases of 2,5-) -3- methyl -3- cyclohexene -1,2- dicarboxylic acid dianhydrides The combination of acid anhydride compound or above compound.
The tetracarboxylic dianhydride's compound indicated to formula (a-3-6) by formula (a-3-1) is as follows.
In formula (a-3-5), A1Indicate the bivalent group containing aromatic rings;R indicates 1 to 2 integer;A2And A3Can be identical Or it is different, and respectively can independently indicate-H or alkyl.The concrete example of tetracarboxylic dianhydride's compound indicated by formula (a-3-5) includes At least one of the compound indicated by formula (a-3-5-1) to formula (a-3-5-3).
In formula (a-3-6), A4Indicate the bivalent group containing aromatic rings;A5And A6Can be identical or different, and respectively independent Expression-H or alkyl.The tetracarboxylic dianhydride's compound indicated by formula (a-3-6) is preferably the chemical combination indicated by formula (a-3-6-1) Object.
The concrete example of fluorine-containing tetracarboxylic dianhydride's compound may include, but are not limited to bis- (the trifluoromethyl) -9H- hexichol of 9,9- And tetracarboxylic dianhydride's compound or above-mentionedization shown in the -2,3,6,7- tetracarboxylic dianhydrides that mutter, following formula (a-3-7) to formula (a-3-13) Close the arbitrary combination of object:
In formula (a-3-7), A7And A8It can be identical or different, and respectively represent hydrogen atom, alkyl, fluorine atom or three Methyl fluoride, wherein A7And A8At least one of be fluorine atom or trifluoromethyl.
Preferably, other tetracarboxylic dianhydride's compounds (a3) including but not limited to 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, 1,2,4,5- cyclopentanetetracarboxylics dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydrides, Shuan Huan &#91;2.2.1&#93;Heptane -2,3,5,6- tetracarboxylic dianhydrides, 7- oxabicyclos &#91;2.2.1&#93;Heptane -2,3,5,6- tetracarboxylic dianhydrides, Shuan Huan &#91;2.2.2&#93;Octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, 8- thias are double Huan &#91;3.2.2&#93;Nonane -2,3,6,7- tetracarboxylic dianhydrides, 3,4- dicarboxyl -1,2,3,4- naphthane -1- ambers acid dianhydride, benzene are equal Tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyltetracaboxylic dianhydrides, 3,3 ', 4,4 '- Biphenyl sulfone tetracarboxylic dianhydride, bis- (the trifluoromethyl) -9H- dibenzo of 9,9- mutter -2,3,6,7- tetracarboxylic dianhydrides or formula (a-3- Or tetracarboxylic dianhydride's compound etc. shown in formula (a-3-10) 8).Other tetracarboxylic dianhydride's compounds (a3) can be used alone or Person's combination is a variety of to be used.
Total mole number based on diamines component (b) is 100 moles, and the usage amount range of tetracarboxylic dianhydride's component (a) is preferable It is 20 moles to 200 moles;More preferably 30 moles to 120 moles.
Diamines component (b)
Diamines component (b) can be selected from aliphatic diamine compound, alicyclic diamine compound, aromatic diamine chemical combination Object, diamine compound or fluorine-containing diamine compound etc. as shown in following formula (b-1) to (b-15).
Aliphatic diamine compound is including but not limited to 1,2- diamino-ethanes, bis- amido propane of 1,3-, bis- amidos of 1,4- Butane, 1,5- diaminopentanes, 1,6- phenylenediamines, 1,7- diamines base heptane, bis- amido octanes of 1,8-, bis- amido nonyls of 1,9- Alkane, bis- amido decane of 1,10-, 4,4 '-diamines base heptanes, bis- amido -2,2- dimethylpropanes of 1,3-, bis- amido -2,5- of 1,6- Dimethylhexane, bis- amido -2,5- dimethyl heptanes of 1,7-, bis- amido -4,4- dimethyl heptanes of 1,7-, bis- amido -3- of 1,7- Methyl heptane, bis- amido -5- methylnonanes of 1,9-, bis- amido dodecanes of 2,11-, bis- amido octadecanes of 1,12-, the bis- (3- of 1,2- Amido propoxyl group) ethane etc..
Alicyclic diamine compound is including but not limited to 4,4 '-two amido dicyclohexyl methyl hydrides, 4,4 '-two amidos -3,3 ' - Dimethyidicyclohexyl amine, 1,3- diamines butylcyclohexane, 1,4- diamines butylcyclohexane, isophorone diamine, two ring penta 2 of tetrahydrochysene Alkene diamines, San Huan &#91;6.2.1.02,7&#93;Endecatylene dimethyl-p-phenylenediamine, 4,4 '-di-2-ethylhexylphosphine oxides (cyclo-hexylamine) etc..
Aromatic diamine compound is including but not limited to 4,4 '-two aminodiphenylmethanes, 4,4 '-two amido diphenyl second Alkane, 4,4 '-two amido diphenyl sulfones, 4,4 '-two amido benzanilides, 4,4 '-two amido diphenyl ethers, 3,4 '-two amidos Diphenyl ether, bis- amido naphthalenes of 1,5-, 5- amidos -1- (4 '-aminocarbonyl phenyl) -1,3,3- trimethyl hydrogen indenes, 6- amidos -1- (4 '-amine Base phenyl) -1,3,3- trimethyl hydrogen indenes, hexahydro -4,7- first bridges Asia hydrogen indenyl dimethylene diamines, 3,3 '-two amido hexichol first Bis- (the 4- amidos phenoxy group) benzene of ketone, 3,4 '-two aminobenzophenones, 4,4 '-two aminobenzophenones, 1,4-, bis- (the 4- amine of 1,3- Phenoxyl) benzene, bis- (the 3- amidos phenoxy group) benzene of 1,3-, bis- (4- the aminocarbonyl phenyls) -10- hydrogen anthracenes of 9,9-, bis- (the 4- amidos of 9,10- Phenyl) En &#91;9,10-bis(4-aminophenyl)anthracene&#93;, bis- (4- aminocarbonyl phenyls) Fluorene of bis- amido Fluorene, 9,9- of 2,7-, 4,4 '-methylene-bis- (2- chloroanilines), 4,4 '-(p-phenylene isopropylidene) dianils, 4,4 '-(- phenylenes different sub- third Base) dianil, 5-&#91;4- (4- pentanes butylcyclohexyl) Huan Jiji &#93;Two amido benzene { 5-&#91 of phenyi-methylene -1,3-;4-(4-n- pentylcyclohexyl)cyclohexyl&#93;Phenylmethylene-1,3-diamino benzene }, the bis- &#91 of 1,1-;4-(4- Amido phenoxy group) Ben Ji &#93;- 4- (4- ethylphenyls) hexamethylene { 1,1-bis&#91;4-(4-aminophenoxy)phenyl&#93;-4-(4- Ethylphenyl) cyclohexane } etc..
Diamine compound is as follows shown in formula (b-1) to formula (b-15):
In formula (b-1), B1Expression-O-, B2It indicates the base with steroid (cholesterol (steroid)) skeleton, the alkyl that carbon number is 2 to 30 or is derived from pyridine, pyrimidine, three The univalent perssad of the nitrogen atoms cyclic structure such as piperazine, piperidines or piperazine.
The concrete example of the compound indicated by formula (b-1) includes but not limited to bis- aminocarbonyl phenyl Ethyl formate (2,4- of 2,4- Diaminophenyl ethyl formate), bis- aminocarbonyl phenyl Ethyl formate (3,5-diaminophenyl ethyl of 3,5- Formate), bis- aminocarbonyl phenyl propyl formates of 2,4- (2,4-diaminophenyl propyl formate), bis- amidos of 3,5- Phenyl propyl formate (3,5-diaminophenyl propyl formate), two amido benzene (1- of 1- dodecyloxies -2,4- Dodecoxy-2,4-diaminobenzene), two amido benzene (1-hexadecoxy-2,4- of 1- hexadecane epoxides -2,4- Diaminobenzene), two amido benzene (1-octadecoxy-2,4-diaminobenzene) of 1- octadecane epoxides -2,4-, by At least one of or above compound combination in the compound that formula (b-1-1) is indicated to formula (b-1-4).
The compound indicated to formula (b-1-4) by formula (b-1-1) is as follows:
In formula (b-2), B1With the B in formula (b-1)1It is identical, B3And B4It is respectively independent to indicate bivalent aliphatic ring, divalent virtue Fragrant race's ring or divalent heterocyclic group;B5Indicate that alkoxy, cyano or halogen that alkyl, carbon number that carbon number is 3 to 18 are 3 to 18 are former Son.
The concrete example of the compound indicated by formula (b-2) includes the chemical combination indicated to formula (b-2-8) by following formula (b-2-1) It is at least one of in object:
In formula (b-3), B6Respectively independently indicate the alkyl, carbon number that acyl group, carbon number that hydrogen atom, carbon number are 1 to 5 are 1 to 5 For 1 to 5 alkoxy or halogen atom, and the B in each repetitive unit6Can be identical or different;U indicates integer of 1 to 3.
The concrete example of the compound indicated by formula (b-3) includes when u is 1:P- diamines benzene, m- diamines benzene, o- diamines Benzene or 2,5- toluenediamines etc.;When u is 2:4,4 '-benzidines, 2,2 '-dimethyl -4,4 '-benzidine, 3, 3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 2,2 '-two chloro- 4,4 '-two amidos Biphenyl, 3,3 '-two chloro- 4,4 '-benzidines, 2,2 ', 5,5 '-four chloro- 4,4 '-benzidines, 2,2 '-two chloro- 4,4 '- Two amidos -5,5 '-dimethoxy-biphenyl or bis- (trifluoromethyl) biphenyl of 4,4 '-two amidos -2,2 '-etc.;Or when u is 3:1,4- Bis- (4 '-aminocarbonyl phenyl) benzene etc..
It includes p- diamines benzene, 2,5- toluenediamines, 4,4 '-that the concrete example of the compound indicated by formula (b-3), which is preferably, Benzidine, 3,3 '-dimethoxy-4 's, bis- (4 '-aminocarbonyl phenyl) benzene of 4 '-benzidines, 1,4- or above compound Combination.
In formula (b-4), k be 2 to 12 integer.
In formula (b-5), w indicates 1 to 5 integer.The compound indicated by formula (b-5) is preferably 4,4 '-two amidos-hexichol Base thioether.
In formula (b-6), B7And B9It is respectively independent to indicate bivalent organic group, and B7And B9Can be identical or different;B8It indicates The bivalent group of cyclic structure derived from nitrogen atoms such as pyridine, pyrimidine, triazine, piperidines or piperazines.
In formula (b-7), B14Indicate oxygen atom or sub- cyclohexyl;B15Indicate methylene;B16Indicate phenylene or sub- hexamethylene Alkyl;B17Indicate hydrogen atom or heptyl.
The concrete example of the compound indicated by formula (b-7) includes the compound indicated by formula (b-7-1), by formula (b-7-2) The combination of the compound or above compound of expression:
The compound indicated to formula (b-15) by formula (b-8) is as follows.
Fluorine-containing diamine compound is preferably selected from the bis- &#91 of 2,2-;4- (4- amidos phenoxy group) Ben Ji &#93;-1,1,1,3,3,3- The bis- &#91 of hexafluoropropane, 2,2-;4- (3- amidos phenoxy group) Ben Ji &#93;The bis- &#91 of -1,1,1,3,3,3- hexafluoropropane, 2,2-;3- (4- amido benzene Oxygroup) Ben Ji &#93;The bis- &#91 of -1,1,1,3,3,3- hexafluoropropane, 2,2-;3- (3- amidos phenoxy group) Ben Ji &#93;- 1,1,1,3,3,3- hexafluoros Bis- (4- the aminocarbonyl phenyls) -1,1,1,3,3,3- hexafluoropropane of propane, 2,2-, bis- (3- the aminocarbonyl phenyls) -1,1,1,3,3,3- of 2,2- Bis- (3- amido -4- the hydroxy phenyls) -1,1,1,3,3,3- hexafluoropropane of hexafluoropropane, 2,2-, bis- (tetra- fluoro- 4- amine of 2,3,5,6- Base phenyl) ether, bis- (tetra- fluoro- 4- aminocarbonyl phenyls of 2,3,5,6-) thioethers, 2,2'Bis- (trifluoromethyl) -4,4'Benzidine, 3,3'Bis- (trifluoromethyl) -4,4'Diamine compound or above-mentionedization shown in benzidine, formula (b-16) to formula (b-43) Close the arbitrary combination of object.
Above-mentioned diamines component can individually a kind of use or mixing plural number kind use.Diamines component preferably includes but unlimited In 1,2- diamino-ethanes, 4,4 '-two amido dicyclohexyl methyl hydrides, 1,4- diamines butylcyclohexane, 4,4 '-two amido diphenylmethyls Alkane, 4,4 '-two amido diphenyl ethers, 5-&#91;4- (4- pentanes butylcyclohexyl) Huan Jiji &#93;Two amido benzene of phenylmethylene -1,3-, The bis- &#91 of 1,1-;4- (4- amidos phenoxy group) Ben Ji &#93;It is -4- (4- ethylphenyls) hexamethylene, bis- aminocarbonyl phenyl Ethyl formates of 2,4-, p- Diamines benzene, m- diamines benzene, o- diamines benzene, 4,4 '-benzidines, the bis- &#91 of 2,2-;4- (4- amidos phenoxy group) Ben Ji &#93;-1,1, Bis- (3- the aminocarbonyl phenyls) -1,1,1,3,3,3- hexafluoropropane of 1,3,3,3- hexafluoropropane, 2,2-, bis- (tetra- fluoro- 4- amine of 2,3,5,6- Base phenyl) ether, 2,2'Bis- (trifluoromethyl) -4,4'Benzidine or formula (b-1-1), formula (b-1-2), formula (b-2- 1), shown in formula (b-2-6), formula (b-7-1), formula (b-23), formula (III-25), formula (b-26), formula (b-27) or formula (b-33) Diamine compound.
The manufacturing method of polymer (A)
The method for preparing polyamic acid resin
The preparation method of polyamic acid resin comprises the steps of:First mixture is dissolved in solvent, wherein mixture Including tetracarboxylic dianhydride's component (a) and diamines component (b), and polymerisation is carried out up to 1 under 0 DEG C to 100 DEG C of temperature condition Hour was to 24 hours.Then, above-mentioned reaction solution is evaporated under reduced pressure with evaporator, you can polyamic acid resin is obtained, Or pour into above-mentioned reaction solution in a large amount of lean solvent, to obtain a precipitate.Then, in the way of being dried under reduced pressure It is dried the precipitate, you can obtain polyamic acid resin.
Solvent used in the polymerization can be identical or different with the solvent in flexible base plate constituent, and for polymerizeing Solvent in reaction is not particularly limited, as long as can dissolve reactant and product.Preferably, solvent includes but not It is limited to (1) non-proton system's polar solvent:N-methyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, Dimethyl sulfoxide (DMSO), gamma-butyrolacton, 4-methyl urea or hexamethylphosphoric acid triamide etc.;(2) phenol system solvent:M-cresol, dimethylbenzene Phenol, phenol or halogenated phenols etc..Preferably, total usage amount based on mixture is 100 parts by weight, solvent used in the polymerization Usage amount ranging from 200 parts by weight to 2,000 parts by weight;More preferably 300 parts by weight are to 1,800 parts by weight.
Particularly, in above-mentioned polymerisation, solvent can and with suitable lean solvent, as long as not allowing polyamic acid resin to analyse Go out.The lean solvent can be individually a kind of or mixes plural number kind use, and lean solvent is including but not limited to (1) alcohols:First Alcohol, ethyl alcohol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4- butanediols or triethylene glycol etc.;(2) ketone:Acetone, methyl Ethyl ketone, methyl iso-butyl ketone (MIBK) or cyclohexanone etc.;(3) esters:Methyl acetate, ethyl acetate, butyl acetate, diethy-aceto oxalate, Diethyl malonate or glycol ethyl ether acetate etc.;(4) ethers:Anaesthetie Ether, Ethylene glycol methyl ether, ethylene glycol ethyl Ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol diformazan Base ether etc.;(5) halogenated hydrocarbons:Dichloromethane, 1,2- dichloroethanes, 1,4- dichloroetane, trichloroethanes, chlorobenzene or o- dichloro Benzene etc.;(6) hydro carbons:Tetrahydrofuran, hexane, heptane, octane, benzene, toluene or dimethylbenzene etc.;Or the arbitrary combination that (7) are above-mentioned.Compared with Goodly, total usage amount based on diamines component is 100 parts by weight, usage amount ranging from 0 parts by weight of lean solvent to 60 parts by weight; More preferably, the usage amount of lean solvent ranging from 0 parts by weight are to 50 parts by weight.
The method for preparing polyimide resin
The preparation method of polyimide resin comprises the steps of:Mixture is dissolved in solvent, wherein mixture packet Tetracarboxylic dianhydride's component (a) and diamines component (b) are included, polymerisation is carried out and forms polyamic acid resin, and in dehydrating agent and touch It in the presence of matchmaker, further heats and carries out dehydration closed-loop reaction so that the amide acid functional group transformation generated when polymerisation At acid imide functional group (i.e. imidizate).
Polymerisation and dehydration closed-loop reaction can adopt the reaction temperature and reaction time that fields operated in the past.Preferably The operating temperature range on ground, polymerisation is 0 DEG C to 100 DEG C.Preferably, the ranging from 1 hour operating time of polymerisation is extremely 24 hours.Preferably, the operating temperature range of dehydration closed-loop reaction is 30 DEG C to 200 DEG C, and when the operation of dehydration closed-loop reaction Between ranging from 0.5 hour to 50 hours.
Can be identical as the solvent in flexible base plate constituent for the solvent in dehydration closed-loop reaction, so it will not be repeated. Preferably, the usage amount based on polyamic acid resin is 100 parts by weight, the usage amount model for the solvent in dehydration closed-loop reaction It encloses for 200 parts by weight to 2,000 parts by weight, more preferably, usage amount ranging from 300 weights for the solvent in dehydration closed-loop reaction Part is measured to 1,800 parts by weight.
For the dehydrating agent in dehydration closed-loop reaction selected from (1) anhydride compound:Acetic anhydride, propionic andydride or trifluoro Acetic anhydride etc..It is 1 mole based on polyamic acid resin, ranging from 0.01 mole to 20 moles of the usage amount of dehydrating agent.For taking off Catalyst in water ring-closure reaction is selected from (1) pyridine compounds and their:Pyridine, trimethylpyridine or lutidines etc.;(2) three Grade aminated compounds:Triethylamine etc..It is 1 mole based on dehydrating agent, ranging from 0.5 mole to 10 moles of the usage amount of catalyst.
The polymer (A) of the present invention is according to gel permeation chromatography (Gel Permeation Chromatography, GPC) the measured weight average molecular weight through polystyrene conversion is 10,000 to 90,000, preferably It is 12,000 to 75,000, more preferably 15,000 to 60,000.
Solvent (B)
The concrete example of solvent (B) includes but not limited to n-methyl-2-pyrrolidone, gamma-butyrolacton, butyrolactam, 4- Hydroxy-4-methyl-2-pentanone, ethylene glycol single methyl ether, butyl lactate, butyl acetate, methoxy methyl propionate, ethoxy-propionic acid Ethyl ester, Ethylene glycol methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol n-butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol two Methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether second Acid esters, diethylene glycol monoethyl ether acetic acid esters or N,N-dimethylformamide or DMAC N,N' dimethyl acetamide (N, N-dimethyl Acetamide) etc..Solvent (B) can be used alone or combine a variety of use.
Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of solvent (B) is 200 to 2000 parts by weight, compared with Good is 250 to 1800 parts by weight, and more preferably 300 to 1500 parts by weight.
Additive (C)
In the range of not influencing effect of the present invention, flexible base plate also optionally adds additive with constituent (C), wherein additive (C) includes but not limited to filler, plasticizer, weather resisting agent, viscosity-controlling agent, surface conditioning agent, antioxygen Agent, antifoaming agent, colorant, thermal stabilizer, adherence auxiliary agent and mould release etc..Additive can be used used in fields .
Filler include but not limited to silica (trade name such as IPA-ST (grain size 12nm), EG-ST (grain size 12nm), IPA-ST-L (grain size 45nm), IPA-ST-ZL (grain size 100nm), Nissan Chemical manufacture), aluminium oxide (aluminium Oxide), talcum, calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, or combinations thereof.
Antioxidant includes but not limited to that (trade name such as BHT, Tokyo chemical conversion industry share have dibutyl hydroxy toluene Limit company (Tokyo Chemical Industry (TCI) Co., Ltd.) manufacture), 2,6-, bis- third butylphenols, or combinations thereof.
Antifoaming agent includes but not limited to silicon systems antifoaming agent (trade name such as SH-203, the beautiful DOW CORNING (Toray-Dow in east Corning) limited liability company manufacture), acetylenediol system antifoaming agent (trade name such as Surfynol DF-100D, Surfynol DF-37, day letter chemistry manufacture), silicon systems antifoaming agent containing fluorine atom (trade name such as FA-630, SHIN-ETSU HANTOTAI's chemistry manufacture) or its group It closes.
Additive (C) can be used alone or combine a variety of use.
Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of additive (C) can be 0.1 to 40 parts by weight, And preferably 1 parts by weight are to 30 parts by weight.
<The Zhi Zaofangfa &gt of flexible base plate constituent;
The manufacturing method of the flexible base plate constituent of the present invention is not particularly limited, and general mixed method can be used To prepare.For example, first the polymer being prepared in the above described manner (A) and solvent (B) are uniformly mixed and form mixture. Then, it is selectively added additive (C), dissolving is finally continued stirring until with agitating device.
At 25 DEG C, the viscosity of flexible base plate of the invention constituent can be adjusted according to each component ratio of constituent Whole, viscosity ranging from 100cps to 20000cps, in a preferable example, the viscosity of flexible base plate constituent can be 120cps to 18000cps, in one more preferably example, the viscosity of flexible base plate constituent can be 150cps to 15000cps.
<The Xing Chengfangfa &gt of flexible base plate;
The flexible base plate of the present invention is formed by above-mentioned flexible base plate constituent.
Specifically, the flexible base plate of the present invention can be coated on constituent on base material by the generation type of flexible base plate, After drying process and cure process, then it is detached from from base material.
Coating method can adopt known mode, such as by rotary coating, cast coat or print roll coating coating method, therefore It repeats no more.Drying process can adopt known mode, it is therefore intended that remove solvent.The operating temperature range of drying process Preferably 50 DEG C to 200 DEG C, the time is 1 minute to 1 hour.Known mode can be used in cure process, it is therefore intended that will be remaining Solvent completely removes and flexible base plate is made to form finer and close structure, and the operating temperature range of cure process is preferably 150 DEG C To 500 DEG C, the time is 10 minutes to 2 hours.
The mode of disengaging can adopt known way, for example, directly tearing off flexible base plate from substrate, using dry ecthing mode Substrate is removed or is removed substrate using wet etching mode etc..
Base material includes but not limited to alkali-free glass, soda-lime glass, the hard glass (Pai Lesibo for liquid crystal display device Glass), quartz glass or Silicon Wafer.
The flexible base plate of the present invention is applicable to flexible liquid crystal display or e-book.
The present invention will be described further with regard to following embodiment, however, it should be noted that such embodiment is only to illustrate to say It is bright, and it is not necessarily to be construed as the limitation that the present invention is implemented.
<Shi Shili >
By the synthesis example for the compound (a1) that formula (a-1) indicates
Illustrate the synthesis example 1 to 8 of the compound (a1) indicated by formula (a-1) below:
Synthesis example 1
By thermometer, return duct and magnetite blender in 200 milliliters of glass reaction container, in a nitrogen environment, incite somebody to action It, will be in reaction vessel after 22.11 grams of chlorination trimellitic anhydride (105 mMs) is dissolved in 25 grams in reaction vessel of acetonitrile Temperature is cooled to 5 DEG C.Later, 7.47 grams of hexamethylene-Isosorbide-5-Nitrae-diyl dimethanol (50 mMs, referred to as a-1) is dissolved in 30 Gram acetonitrile in, and 8.3 grams of the pyridine (105 mMs) as hydrochloric acid agent for capturing is added.By above-mentioned solution at 5 DEG C, It is instilled in one hour in chlorination trimellitic acid anhydride solution above-mentioned.35 DEG C of temperature is kept after dripping off and continues stirring 5 hours, with Product is made.After above-mentioned product is filtered, above-mentioned product is cleaned with acetonitrile, to obtain white crystals.By above-mentioned white Drying 24 hours at the reduced pressure atmosphere of 5mmHg and 50 DEG C are crystallized, tetracarboxylic dianhydride's compound (a1-1) can be made (i.e. such as formula (a-1-1) compound represented).
Synthesis example 2 to 8
Synthesis example 2 to 8 is prepared respectively with the step identical as synthesis example 1, difference be in:Used in change Classes of compounds, usage amount or reaction condition (as shown in table 1).
Compound in table 1 corresponding to label is as follows.
&#91;Table 1&#93;
The synthesis example of polymer (A)
Illustrate synthesis example A-1-1 to A-1-7, the synthesis example A-2-1 to A-2-7 of polymer (A) below and compares synthesis Example A ' -1-1 to A ' -1-2, A ' -2-1 to A ' -2-2:
Synthesis example A-1-1
Setting nitrogen inlet, blender, condenser pipe and thermometer on four cervical vertebra bottles of 500 milliliters of a volume, and import Nitrogen.Then, the p- diamines benzene (referred to as b-1) and 70 grams of N- methyl -2- pyrrolidines of 5.41 grams (0.05 mole) is added Ketone (referred to as NMP), and stirring is extremely dissolved at room temperature.Then, be added 3.69 grams (0.0075 mole) by formula (a-1-1) table Compound (the a2) (abbreviation of the compound (a1) (referred to as a1-1), 12.0 grams (0.04 mole) shown indicated by formula (a-2-1) For a2-1), the compound (a2) (referred to as a2-4) indicated by formula (a-2-12) of 0.89 gram (0.0025 mole) and 30 grams NMP, and at room temperature react 2 hours.After reaction, reaction solution is poured into 1500 milliliters of water, polymerization is precipitated Object filters the polymer of gained, and the step of repeating to clean and filter with methanol is three times.Later, product is placed in vacuum It in baking oven, and is dried with temperature 60 C, you can obtain polymer (A-1-1).
Synthesis example A-1-2 to A-1-7 and compare synthesis example A-1 ' -1 to A-1 ' -2
Synthesis example A-1-2 to A-1-7 and to compare synthesis example A ' -1-1 to A ' -1-2 be with identical with synthesis example A-1-1 Step prepares polymer (A-1-2) to (A-1-7) and (A ' -1-1) to (A ' -1-2) respectively, and its difference be in: Change the type and its usage amount (as shown in table 2) of monomer.
Synthesis example A-2-1
Setting nitrogen inlet, blender, heater, condenser pipe and thermometer on four cervical vertebra bottles of 500 milliliters of a volume, And import nitrogen.Then, 4, the 4 '-two aminodiphenylmethanes (referred to as b-2) of addition 0.50 gram (0.025 mole), 1.05 The compound (referred to as b-3) indicated by formula (b-7-2) of gram (0.025 mole) and 70 grams of NMP, and stir at room temperature To dissolving.Then, be added 4.22 grams (0.0075 mole) the compound (a1) (referred to as a1-8) indicated by formula (a-1-24), The compound (a2) (referred to as a2-4) indicated by formula (a-2-12) of 0.89 gram (0.04 mole) and 30 grams of NMP.Room temperature After lower reaction 6 hours.After reaction, 97 grams of NMP, 5.61 grams of acetic anhydride and 19.35 grams of pyridine is added to above-mentioned In reaction solution, 55 DEG C are warming up to, and persistently stir 2 hours, to carry out dehydration closed-loop reaction.After reaction, by reaction solution Pour into 1500 milliliters of water, polymer is precipitated, filter gained polymer, and with methanol repeat clean and filter Step is three times.Later, product is placed in vacuum drying oven, and is dried with temperature 60 C, you can obtain polymer (A-2-1).
Synthesis example A-2-2 to A-2-7 and compare synthesis example A-2 ' -1 to A-2 ' -2
Synthesis example A-2-2 to A-2-7 and to compare synthesis example A ' -2-1 to A ' -2-2 be with identical with synthesis example A-2-1 Step prepares polymer (A-2-2) to (A-2-7) and (A ' -2-1) to (A ' -2-2) respectively, and its difference be in: The type and its reaction temperature of usage amount and dehydration closed-loop reaction of change monomer and reaction time (as shown in table 3).
Compound in table 2, table 3 corresponding to label is as follows.
&#91;Table 2&#93;
&#91;Table 3&#93;
The embodiment of flexible base plate constituent
Embodiment 1
The NMP of polymer (A-1-1) and 200 parts by weight of the synthesis example A-1-1 of 100 parts by weight are weighed, and at room temperature It is stirred, you can the flexible base plate constituent of embodiment 1 is made.
The flexible base plate of gained is evaluated with constituent with following evaluation methods, and the results are shown in Table 4.
Embodiment 2 to 14 and comparative example 1 to 4
Embodiment 2 to 14 and comparative example 1 to 4 use preparation method identical with the flexible base plate constituent of embodiment 1, The difference is that embodiment 2 to 14 and comparative example 1 to 4 change the type and usage amount of raw material in flexible base plate constituent, It is formulated and evaluation result is respectively as shown in table 4, table 5.
Compound in table 4 and table 5 corresponding to abbreviation is as follows.
&#91;Table 4&#93;
&#91;Table 5&#93;
<Ping Jiafangshi >
Phase difference
By the flexible base plate constituent of above-described embodiment 1 to 14 and comparative example 1 to 4 in a manner of rotary coating, coating On the glass substrate that size is 100mm × 100mm.Then, it is 10 μm with 80 DEG C of pre-baked thickness that can be formed after twenty minutes Pre-baked film.Then, it is baked after being carried out at 260 DEG C, after 30 minutes, you can be made one and contain glass substrate and flexible base plate Laminate.The optical material check device (model RETS-100) manufactured by great Zhong electronics corporations, under room temperature (20 DEG C), Pass through the light measurement that wavelength is 550nm:The refractive index nx of the X-direction of flexible base plate on laminate, the refractive index of Y direction The refractive index nz of ny and Z-direction.Also, according to the refractive index nx of X-direction, the refractive index ny of Y direction and Z-direction Refractive index nz and the thickness (d) of film the phase difference (Rth) of thickness direction is calculated according to following formula.
Rth (nm)=s &#91;nz-(nx+ny)/2&#93;×d
Also, the value of gained is scaled value when thickness (d) is 10 μm, and is evaluated according to following benchmark:
◎:Rth < 10nm
○:10nm≤Rth < 50nm
△:50nm≤Rth < 200nm
╳:200nm≦Rth
<Ping Jiajieguo >
Learnt by table 4 and table 5, when the polymer (A) in flexible base plate constituent tetracarboxylic dianhydride's component (a) not When including simultaneously the compound (a1) indicated by formula (a-1) and compound (a2) (comparative example 1 to 4) indicated by formula (a-2), The phase difference for being formed by flexible base plate is bad.
In addition, when tetracarboxylic dianhydride's component (a) of the polymer (A) in flexible base plate constituent includes having such as formula (a-1-x) it when the compound of structure shown in is as compound (a1) (embodiment 1 to 3,5,9 to 13), is then formed by soft The phase difference of substrate is more preferably.
In addition, when tetracarboxylic dianhydride's component (a) of the polymer (A) in flexible base plate constituent includes in formula (a-1) R when indicating compound that carbon number is 1 to 3 alkylidene as compound (a1) (embodiment 1,5 to 7,9,12 to 14), then institute The phase difference of the flexible base plate of formation is also more preferably.
In conclusion in the flexible base plate constituent of the present invention, because of the tetracarboxylic acid in the mixture of formation polymer (A) Acid dianhydride component (a) includes the compound (a1) indicated by formula (a-1) and the compound (a2) indicated by formula (a-2), therefore It can improve the bad problem of phase difference using the flexible base plate obtained by the flexible base plate constituent.
On the other hand, in flexible base plate constituent of the invention, because of the tetracarboxylic acid in the mixture of formation polymer (A) Acid dianhydride component (a) includes indicating that carbon number is 1 with the R in the compound of structure or formula (a-1) as shown in formula (a-1-x) To 3 alkylidene compound as compound (a1), and make the phase difference of flexible base plate more preferably, therefore soft suitable for manufacturing Liquid crystal display or e-book.
Although the present invention is disclosed as above with embodiment, however, it is not to limit the invention, any technical field Middle technical staff, without departing from the spirit and scope of the present invention, when can make a little change with retouching, therefore the present invention protection Range is when subject to as defined in claim.

Claims (7)

1. a kind of flexible base plate constituent, which is characterized in that including:
Polymer (A);And
Solvent (B),
Wherein, the polymer (A) be by mixture react and obtain, the mixture include tetracarboxylic dianhydride's component (a) and Diamines component (b),
Tetracarboxylic dianhydride's component (a) includes by formula (a-1) compound represented (a1) and the chemical combination shown in formula (a-2) Object (a2):
In formula (a-1),
R respectively independently indicates that carbon number is 1 to 6 alkylidene;
RXIndicate that bivalent aliphatic cyclic hydrocarbon radical, the bivalent aliphatic cyclic hydrocarbon radical are to be unsubstituted or through halogen atom, straight-chain hydrocarbon Base or the bilvalent radical of branched alkyl substitution,
In formula (a-2),
R1Indicate the alkyl that hydrogen atom or carbon number are 1 to 6;
R2It is respectively independent to indicate hydrogen atom, methyl or ethyl group.
2. flexible base plate constituent according to claim 1, wherein in the formula (a-1), the RxWith such as formula (a-1-x) structure shown in:
In formula (a-1-x),
M indicates 0 to 4 integer;
RZThe branched alkyl or multiple that respectively the independent straight-chain alkyl, carbon number for indicating that halogen atom, carbon number are 1 to 4 is 1 to 4 Several RZIt is interconnected to form cyclic structure.
3. flexible base plate constituent according to claim 1, wherein in the formula (a-1), the respective independent tables of the R Show that carbon number is 1 to 3 alkylidene.
4. flexible base plate constituent according to claim 1, wherein always rubbing based on tetracarboxylic dianhydride's component (a) Your number is 100 moles, and the usage amount of the compound (a1) indicated by formula (a-1) is 15 to 85 moles, described by formula (a-2) The usage amount of the compound (a2) of expression is 15 to 85 moles.
5. flexible base plate constituent according to claim 1, wherein total usage amount based on the polymer (A) is The usage amount of 100 parts by weight, the solvent (B) is 200 to 2000 parts by weight.
6. flexible base plate constituent according to claim 1, wherein at 25 DEG C, the flexible base plate constituent Viscosity is 100cps to 20000cps.
7. a kind of flexible base plate, which is characterized in that include flexible base plate constituent according to any one of claims 1 to 6.
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CN102276562A (en) * 2011-05-28 2011-12-14 南昌大学 1,2,2-trimethyl cyclopentyl alicyclic structure-containing dianhydride and preparation method thereof

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